- A juvenile hormone analogs of the preparation method
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The invention relates to the field of insecticides, and particularly relates to a preparation method of a juvenile hormone analogue (which comprises S-methoprene and S-hydroprene). The preparation method of the juvenile hormone analogues comprises the following steps of: A. adding (2E, 4E)-11-R-3,7,11-trimethyl-2,4-dodecadienoic acid (R is hydrogen or methoxyl) serving as raw material, an organic alkali catalyst and an organic solvent to a reaction vessel, and starting stirring; B. dropwise adding an organic solvent (the same as the organic solvent in the step A) solution of pyrocarbonate; C. after the addition is completed, reacting at 0-30 DEG C for 0-3 hours; D. adding water to stop reaction, and splitting phases of reaction liquid to obtain an organic phase; E. carrying out reduced pressure concentration and distillation to obtain a product, wherein the steps can also be carried out under the condition that the addition sequences of the pyrocarbonate and an organic strongly-alkaline catalyst are exchanged. The preparation method disclosed by the invention has the advantages of mild reaction condition, high product purity, high yield, environment-friendly and safe route and good industrial prospect.
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Paragraph 0047; 0064-0065
(2017/05/10)
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- Stereoselective synthesis of the insect growth regulator (S)-(+)-hydroprene through Suzuki-Miyaura cross-coupling
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A stereoselective synthesis of the insect growth regulator (S)-(+)-hydroprene has been developed in seven steps with 50% overall yield starting from an easily available bromoester. Through using the Suzuki-Miyaura cross-coupling as the key Csp2-Csp2 bond forming step, high level of stereocontrol of the C2-C3 olefin is achieved.
- Zhang, Shunji,Dong, Huaide,Gui, Jinghan,Tian, Weisheng
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p. 1882 - 1884
(2012/05/05)
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- Preparation of alkyl 3-methylalka-2,4-dienoates from γ,δ-unsaturated β-keto esters via the corresponding conjugated unsaturated 3-enol phosphates
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Methylation of α,β,γ,δ-unsaturated-β-substituted enol phosphates with lithium dimethyl cuprate gave a mixture of (2E,4E)- and (2Z,4E) alkyl 3- methylalka-2,4-dienoates and unsubstituted alkyl alka-2,4-dienoates. An improved synthesis is described for ethyl β-safranate and the insect growth regulator hydroprene.
- Moorhoff, Cornelis M.,Schneider, David F.
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p. 3279 - 3290
(2007/10/03)
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- Combined Biochemical and Electrochemical Approach to Chiral C10-Components for Juvenoid Synthesis, and Preparation of (2E,4E,7S)Stereoisomers of Metoprene and Hydroprene
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Enantioselective acylation of (RS)-3,7-dimethyl-7-methoxyoctan-1-ol and (RS)-3,7-dimethyl-octan-1-ol with vinyl acetate in the presence of lipase from yeast Candida cylindracea was performed to conversion of 40-50%, and subsequent hydrolysis of the products afforded (S)-(-)-enantiomers of these alcohols with ee of 98-100%. The oxydation of these products by bromine generated by electrolysis in a membraneless device in the system "aqueous NaBr (+NaHCO3)/CH2Cl2" in the presence of 4-substituted 2,2,6,6-tetramethyl-1-oxopiperidinium salts furnished the corresponding (S)-(-)-alkanals. The condensation of the latter with the esters of 3-alkoxycarbonyl-2-methylprop-2-enylphosphonic acids in a heterophase system solid KOH-benzene-tetraoctylammonium bromide yielded samples of metoprene and hydroprene of high configurational purity.
- Gamalevich,Zhdankina,Kryshtal',Nikishin,Ogibin,Serebryakov
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p. 467 - 474
(2007/10/03)
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- Synthesis of S-(+)-hydroprene
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A novel path to S-(+)-hydroprene (1) starting from the technical grade S-(+)-dihydromyrcene (2, e.e. > 50percent) is proposed.The latter was selectively transformed into S-3,7-dimethyloctanal (5) in three steps including hydroalumination.The reactions of 5 with allyl- or methallylmagnesium chloride followed, respectively, either by oxygenation in the presence of PdCl2/CuCl or by ozonolysis, afford S,E-6,10-dimethyl-3-undecen-2-one (7) which was treated with ethoxyethynylmagnesium bromide to give the title juvenile hormone analogue in ca. 23percent overall yield.
- Odinokov, V. N.,Ishmuratov, G. Yu.,Kharisov, R. Ya.,Serebryakov, E. P.,Tolstikov, G. A.
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p. 100 - 101
(2007/10/02)
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- Terpenes in organic synthesis 14. Synthesis of S-(+)-hydroprene from (+)-β-citronellene
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A seven-step synthesis of S-(+)-hydroprene (S-1) in ca. 20percent overall yield starting from S-(+)-3,7-dimethyl-1,6-octadiene (2) of 55 +/- 10percent optical purity is described.The introduction of an optical enhancement step in the synthetic sequence at the stage of S-(-)-3,7-dimethyl-1-octanol (9) raises the optical purity of S-1 from ca. 50percent to ca. 80percent.
- Gamalevich, G. D.,Serebryakov, E. P.
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p. 300 - 306
(2007/10/02)
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- On the stereochemistry of the Horner-Emmons reaction between 3-functionally substituted 2-methyl-2-propenylphosphonates and aliphatic aldehydes 7. Quaternary ammonium phase transfer catalysts in a stereoselective synthesis of esters of 3-methyl-2E,4E-alkadienoic acids
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The reaction of diethyl 3-ethoxycarbonyl-2-methyl-2-propenylphosphonate (1a) with 3-methylbutanal (2) in heterogeneous MOH (solid)-behzene systems in the presence of 5-10 mol.percent of benzyltriethylammonium chloride (BTEAC) gives the reaction product (3) with a higher, for M = K, or lower, for M = Li, ratio of 2E,4E- and 2Z,4E-stereoisomers than that observed in the absence of BTEAC.Tetrabutylammonium bromide (TBAB) as a catalyst of the reaction 1a + 2 -> 3 in the system KOH (solid) - wet benzene leads to a higher : ratio than BTEAC; this ratio grows from 44:56 without TBAB to 80:20 at 100 mol.percent of TBAB.In the latter case...
- Kryshtal', G. V.,Zhdankina, G. M.,Serebryakov, E. P.
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p. 1048 - 1052
(2007/10/02)
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- OZONOLYSIS OF ALKENES AND REACTIONS OF POLYFUNCTIONAL COMPOUNDS. XXXVI. SYNTHESIS OF ETHYL 3,7,10-TRIMETHYL-2E,4E-DODECADIENOATE
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Hydroprene was obtained with an overall yield of 16percent in the form of a 77:23 mixture of 2E,4E and 2Z,4E isomers by ozonolysis of 1,5-dimethyl-1-cyclooctene and selective transformations of the 4-methyl-1,1-dimethoxy-8-oxononane, including ethoxycarbonylmethylenation of the keto group, alkylation of the formyl group by isopropylmagnesium bromide followed by deoxygenation, and allylic bromination-dehydrobromination.The individual 2E,4E isomer was isolated by HPLC.
- Odinokov, V. N.,Kukovinets, O. S.,Zainullin, R. A.,Sultanmuratova, V. R.,Tolstikov, G. A.
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p. 1230 - 1237
(2007/10/02)
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- Stereocontrolled Synthesis of the Insect Growth Regulators - Alkyl (2E,4E)-Dodecadienoates
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The title compounds 1 and 16 were synthesized by condensation of the dianions of β-keto esters 5 and 11 with aldehydes 4, and lithium dialkylcuprate addition to the enol acetate or enol phosphate of unsaturated β-keto esters 8 and 15.The (2E,4E)-dodecadienoate derivatives 1 and 16 were formed in a stereoselective manner.
- Novak, Lajos,Rohaly, Janos,Kolonits, Pal,Fekete, Jenoe,Varjas, Laszlo,Szantay, Csaba
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p. 1173 - 1182
(2007/10/02)
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